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Self-assembly and phase behaviour of PEI : Cationic surfactant aqueous mixtures forming mesostructured films at the air/solution interface

Comas-Rojas, Hansel ; Enríquez-Victorero, Carlos ; Roser, Stephen J. ; Edler, Karen J. LU orcid and Pérez-Gramatges, Aurora (2013) In Soft Matter 9(15). p.4003-4014
Abstract

Self-assembly processes and corresponding phase boundaries depend on the structure of interacting molecules. We have studied the effect of surfactant head-group structure and counterion on the self-assembly processes occurring in aqueous mixtures of the cationic polymer polyethylenimine (PEI) and the cationic surfactants cetyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB) and cetylpyridinium chloride (CPC). Surface tension and conductometric methods were employed, as well as X-ray scattering and reflectometry techniques. The results indicate that the phase behaviour of PEI: Cationic surfactant mixtures under dilute conditions can be tuned by altering head-group and counterion. The surfactant head-group exerts a greater... (More)

Self-assembly processes and corresponding phase boundaries depend on the structure of interacting molecules. We have studied the effect of surfactant head-group structure and counterion on the self-assembly processes occurring in aqueous mixtures of the cationic polymer polyethylenimine (PEI) and the cationic surfactants cetyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB) and cetylpyridinium chloride (CPC). Surface tension and conductometric methods were employed, as well as X-ray scattering and reflectometry techniques. The results indicate that the phase behaviour of PEI: Cationic surfactant mixtures under dilute conditions can be tuned by altering head-group and counterion. The surfactant head-group exerts a greater influence overall, especially over micellization, since the counterion effect is screened at high polymer concentrations. Also, the self-assembly processes occurring at lower surfactant concentrations are not significantly affected by the counterion effect. The variation of surface tension with surfactant concentration shows a particular 'well-like' profile with a distinct break-point that can be directly related to the onset of film formation. Phase diagrams constructed using surface tension, conductivity and Brewster angle microscopy (BAM) data show three different regions where initial interactions, film formation and micellization take place, respectively, characterized by the two main self-assembly boundaries. Based on these results, we propose a molecular interpretation of the aggregation and film formation processes occurring in PEI: Cationic surfactant mixtures under increasing surfactant concentrations within the dilute regime.

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author
; ; ; and
publishing date
type
Contribution to journal
publication status
published
in
Soft Matter
volume
9
issue
15
pages
12 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:84875637027
ISSN
1744-683X
DOI
10.1039/c3sm27541h
language
English
LU publication?
no
id
e5843d9c-e928-456b-9e8e-618aecc3131a
date added to LUP
2023-05-04 18:23:42
date last changed
2023-08-24 10:38:14
@article{e5843d9c-e928-456b-9e8e-618aecc3131a,
  abstract     = {{<p>Self-assembly processes and corresponding phase boundaries depend on the structure of interacting molecules. We have studied the effect of surfactant head-group structure and counterion on the self-assembly processes occurring in aqueous mixtures of the cationic polymer polyethylenimine (PEI) and the cationic surfactants cetyltrimethylammonium bromide (CTAB), cetylpyridinium bromide (CPB) and cetylpyridinium chloride (CPC). Surface tension and conductometric methods were employed, as well as X-ray scattering and reflectometry techniques. The results indicate that the phase behaviour of PEI: Cationic surfactant mixtures under dilute conditions can be tuned by altering head-group and counterion. The surfactant head-group exerts a greater influence overall, especially over micellization, since the counterion effect is screened at high polymer concentrations. Also, the self-assembly processes occurring at lower surfactant concentrations are not significantly affected by the counterion effect. The variation of surface tension with surfactant concentration shows a particular 'well-like' profile with a distinct break-point that can be directly related to the onset of film formation. Phase diagrams constructed using surface tension, conductivity and Brewster angle microscopy (BAM) data show three different regions where initial interactions, film formation and micellization take place, respectively, characterized by the two main self-assembly boundaries. Based on these results, we propose a molecular interpretation of the aggregation and film formation processes occurring in PEI: Cationic surfactant mixtures under increasing surfactant concentrations within the dilute regime.</p>}},
  author       = {{Comas-Rojas, Hansel and Enríquez-Victorero, Carlos and Roser, Stephen J. and Edler, Karen J. and Pérez-Gramatges, Aurora}},
  issn         = {{1744-683X}},
  language     = {{eng}},
  month        = {{04}},
  number       = {{15}},
  pages        = {{4003--4014}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Soft Matter}},
  title        = {{Self-assembly and phase behaviour of PEI : Cationic surfactant aqueous mixtures forming mesostructured films at the air/solution interface}},
  url          = {{http://dx.doi.org/10.1039/c3sm27541h}},
  doi          = {{10.1039/c3sm27541h}},
  volume       = {{9}},
  year         = {{2013}},
}